AI Article Synopsis
- The study focuses on both unsubstituted and substituted -benzyne, revealing that the substituted variants have not been as thoroughly investigated as the unsubstituted form.
- Benchmark calculations for unsubstituted -benzyne were conducted using various density functional theory (DFT) functionals and basis sets, establishing a foundation for evaluating substituted versions.
- Key findings indicate that substitutions near the benzyne ring significantly affect its geometry and energy properties, with distinct influences such as hyperconjugation, resonance, and electrostatics from the substituents.
Article Abstract
-benzyne has been well studied by both experiment and theory. Its substituted variants, however, have been less carefully examined. Benchmark data are computed for unsubstituted -benzyne using several density functional theory functionals and basis sets, up to cc-pVQZ. Optimized geometries for the substituted -benzyne as well as harmonic vibrational frequencies and singlet-triplet splittings are computed using the benchmarked functionals. A proximal ()OH substitution causes a mean θ distortion of +8.1 ± 1.4° from -benzyne. Substituting in the proximal position with F shifts the singlet-triplet splitting by +4.5 ± 0.4 kcal mol from -benzyne. Natural bond orbital analysis, including natural Coulomb electrostatics, elucidates the presence of three influences from the selected substituents: hyperconjugative, resonance, and electrostatic effects.
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| http://dx.doi.org/10.1021/acs.joc.0c01209 | DOI Listing |
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